Composition and method for stimulating plant growth



United States Patent 3,396,007 COMPOSITION AND METHOD FOR STIMULATINGPLANT GROWTH Stanley J. Strycker, Midland, Mich., assignor to The DowChemical Company, Midland, Mich., a corporation of Delaware No Drawing.Original application Sept. 10, 1963, Ser. No. 307,788. Divided and thisapplication Apr. 21, 1966, Ser. No. 560,398

3 Claims. (Cl. 71-77) ABSTRACT OF THE DISCLOSURE The present inventionis directed to methods and compositions for the alteration of the growthof plants. The active agent of these methods and compositions is acompound of the formula NO: R" RSO l IRl ISO-zR wherein R represents adivalent hydrocarbonylene radical selected from the group consisting ofalkylene being of from 2 to 10, inclusive, carbon atoms, Z-butenylene,cyclohexylene, and cyclohexylenedimethylene; R represents a memberselected from the group consisting of loweralkyl being of from 1 to 4,inclusive, carbon atoms, phenyl, and substituted phenyl; and R"represents a member selected from the group consisting of hydrogen andniltro.

CROSS-REFERENCES TO RELATED APPLICATIONS This is a division of copendingapplication Ser. No. 307,788, filed Sept. 10, 1963, which has since beenabandoned in favor of a continuation-in-part application, Ser. No.609,295, filed Jan. 16, 1967.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directedto nitrosulfonamide compound of the formula and to methods andcompositions employing such compound for the modification and alterationof the growth of numerous organisms. In this and succeeding formulae, Rrepresents a divalent hydrocarbonylene radical selected from the groupconsisting of alkylene being of from 2 to 10, inclusive, carbon atoms,Z-butenylene, cyclohexylene, and cyclohexylenedimethylene; R representsa member selected from the group consisting of loweralkyl being of from1 to 4, inclusive, carbon atoms, phenyl, and substituted phenyl; and Rrepresents a member selected from the group consisting of hydrogen andnitro. These novel compounds are oils or crystalline solid materials.They are somewhat soluble in many common organic solvents and of lowsolubility in water.

In the present specification and claims, the term a1- kylene is employedto refer to straight-chain divalent radicals as well as tobranched-chain divalent radicals; and the term substituted phenyl refersto a phenyl radical which is ring substituted with one or moresubstituent moieties selected from the group consisting of halo,loweralkyl, nitro, and carboloweralkoxy. Representative alkyleneradicals include ethylene, propylene, tetramethylene,Z-ethyltrimethylene, heXamethy-lene, nonamethylene,l,8-dimethyloctamethylene, and heptamethylene; and representativesubstituted phenyl radicals include tolyl, xylyl, bromophenyl,dichlorophenyl, tribromophenyl, trimethylphenyl, chloroxylyl,nitrotolyl, dini- 3,396,007 Patented Aug. 6,. 1968 ice The nitration canbe effected by employing any of numerous nitrating agents such as, forexample, nitric acid, fuming nitric acid, a mixture of nitric andsulfuric acid, other mixtures having as a major component nitric acid,nitronium tetrafiuoroborate (that is, NO BF4), and dinitrogenpenttoxide. Preferably, where R is nitro, the fuming nitric acid isemployed.

The reaction is conveniently carried out in the presence of an inertreaction medium, preferably, an organic liquid. Suitable organic liquidsare acetic anhydride, methylene chloride, and nitromethane. However,where R represents nitro, the use of nitrating agent as both reactantand inert liquid reaction medium results in higher yields and ispreferred.

Where R" represents hydrogen, preferred embodiments of the presentmethod include the use of nitric acid (as nitrating agent) in aceticanhydride (as inert liquid reaction medium), the use of nitroniumfiuoroborate in inert liquid reaction medium such as nitromethane ormethylene chloride, and the use of dinitrogen pentoxide in appropriateinert liquid reaction medium, such as chloroform.

The amounts of the reactants to *be employed are not critical, some ofthe desired product compound being obtained when employing the reactantsin any amounts. Where R" represents nitro, the reaction consumes thereactants in amounts which represent one molecular proportion ofhydrocarbonylenedisulfonamide and two molecular proportions of nitratingagent. However, the use of hydrocarbonylenedisulfonamide in an amountwhich representsv one molecular proportion and nitrating agent in anamount which represents an excess of the two molecular proportionsconsumed, such as five to ten molecular proportions of nitrating agent,is preferred. Where R" represents hydrogen, the reaction consumes thereactants in amounts which represent equimolecular proportions; the useof such proportions results in higher yields and is preferred.

The reaction takes place smoothly at temperatures between -20 and 25 C.and preferably at temperatures between 5 and 10 C., with the productionof the desired product in the reaction mixture.

In carrying out the reaction, the reactants are contacted together inany convenient fashion and maintained for a period of time in thereaction temperature range to complete the reaction. Some of the desiredproduct com- --pound is formed immediately upon the contacting of thereactants; however, the yield of the desired product compound isincreased by permitting the reaction mixture to stand fora period oftime.

After the completion of the reaction, the desired product compound canbe separated from the reaction mixture by filtration and/or the reactionmedium removed by distillation or evaporation under subatmosphericpressure. As a result of such operations, the desired product compoundis obtained as a residue. This residue can be used without purificationor can be' purified "by conventional procedures, such as, for example,washing with water, washing with inert liquid reaction medium, orrecrystallization.

3 Where compound of the present invention contains a nitro substituentmoiety on a substituted phenyl radical, such'compound can be prepared ina modified method of the above synthesis. Such modified synthesiscomprises nitrating a hydrocarbonylenedisulfonamide compound wherein thephenyl or substituted phenyl radical bears no .nitro su'bstituent moietyto introduce onto the phenyl or substituted phenyl radicals one or morenitro substituent moieties simultaneously with the introduction of nitromoieties onto the nitrogen atom of the sulfonamide function. Thereaction conditions in such modified methd are essentially the same asthose of the method as herein'before discussed. However, as will beunderstood by those skilled in the art, the preferred amounts of theemployed reactants are those which represent one molecular proportion ofhydrocarbonylenedisulfonamide, and a number of molecular proportions ofnitrating agent equal to the total number of nitro moieties to beintroduced into the hydrocarbonylenedisulfonamide compound. Typically,the nitro substituents on the phenyl or substituted phenyl radicalfollow the conventional substituent position rules.

The following examples illustrate the invention but are not to beconstrued as limiting.

Example 1.N,N-ethylenebis(N-nitrobenzenesulfonamide) A quantity ofturning nitric acid having a specific gravity of 1.5 was cooled to atemperature of about 0 C. N,N- ethylenebis(benzenesulfonamide) (10grams; 0.027 mole) was added to 55 milliliters of the cooled fumingnitric acid. The addition was carried out portionwise over a period oftime so that the temperature of the resulting reaction mixture remainedbelow C. The reaction mix ture was maintained at a temperature of 0 C.for 1 /2 hours with stirring. Thereafter, the reaction mixture was mixedwith a quantity of water at a temperature of 0 C., during which theN,N'-ethylenebis(N-nitrobenzene-sulfonamide) product crystallized in themixture. The mixture was then permitted, as a matter of convenience, tostand for a period of about 60 hours.

The product was separated from the mixture by filtration and dried.After recrystallization from toluene, the product was found to melt,with decomposition, at 157- 157.5 C.

Example 2.N,N-octamethylenebis(N-nitromethanesulfonamide) N,N'octamethylenebis(methanesulfonamide) grams; 0.033 mole) was addedportionwise and with stirring to 80 milliliters of turning nitric acid,having a specific gravity of 1.5 and at a temperature of -2 C. Duringthe addition, the temperature of the resulting reaction mixture rose toabout 3 C. The resulting reaction mixture was stirred for a period of 1hour at a temperature of about 0 C. and then mixed with 800 millilitersof water at a temperature of about 0 C. During the mixing, theN,N'-octamethylenebis(N-nitromethanesulfonamide) product crystallized inthe mixture. The mixture was stirred for about 1 hour, with thetemperature permitted to rise spontaneously to that of room temperature.Thereafter, the product was separated as a residue and dried. Afterseveral recrystallizations from ethanol, the product was found to meltat 7778 C.

Example 3.-N-nitro-N,N'-propylenebis(methanesulfonamide) A quantity ofacetic anhydride is cooled to a temperature of from --10 to C. To 25milliliters of the cooled acetic anhydride are added portionwise over aperiod of time and with stirring 4.4 milliliters of fuming nitric acidhaving a specific gravity of 1.5 (0.1 mole). The addition is carried outso that the temperature of the resulting mixture at no time exceeds 5 C.

Thereafter, a second cooled mixture is similarly prepared from 25milliliters of acetic anhydride at a temperature of 10 to --15 C. and23.0 grams of N,N'- propylenebis(methanesulfonamide) (0.1 mole). Themixture containing thenitric acid is then added to the mixturecontaining the sulfonamide compound, portionwise, over a period of timeso that the temperature of the resulting reaction mixture does not riseabove 5 C. After the addition has been completed, the reaction mixtureis maintained at the temperature range of 0 to 5 C. for 4 hours withstirring. The reaction mixture is thereafter diluted with a quantity ofice water, and the diluted reaction mixture filtered to separate theN-nitro-N,N-pro pylenebis(methanesulfonamide) product which is found tomelt at 108110.5 C. The compound has the following structural formula Ina similar manner, other compounds representative of the presentinvention are prepared as follows.

From N,N'-trimethylenebis(methanesulfonamide) and fuming nitric acid,N,N-trimethylenebis(N-nitro-methanesulfonamide) product melting at66.567 C.

From N,N' 2-butenlyenebis(3,4-bis(carboethoxy)benzenesul fon'amide) andfuming nitric acid, N,N'-2-butenylenebis(3,5 bis(carboethoxy) Nnitrobenzenesulfonamide) product. The product has a molecular weight of744].

From N,N' hexamethylenebis(l-butanesulfonamide) and a mixture of nitricand sulfuric acids, a white crystalline N,Nhexamethylenebis(N-nitro-l-butanesulfonamide) product melting at 6869.5C.

From N,N' 1,4-cyclohexylenebis (pentachlorobenzenesulfonamide) andfuming nitric acid, N,N'-1,4-cyclohexylenebis(pentachloroN-nitrobenzenesulfonamide) product (molecular weight of 829.0).

From N,N' ethylenebis(methanesulfonamide) and fuming nitric acid,N,N-ethylenebis(N-nitromcthanesulfonamide) product melting at 156.5157.0C.

From N,N' 2 butenylenebis(3,5-dimethylbenzenesulfonamide) and fumingnitric acid, N,N'-2-butenylenebis-(N-nitro-3,5-dimethylbenzenesulfonamide) product having a molecularweight of 512.6.

-From N,N' tetramethylenebis(methanesulfonamide) and fuming nitric acid,a white crystalline N,N'-tetramethylenebis(N-nitromethanesulfonamide)product melting at 132-133.5 C.

From N,N'-hexamethylenebis(ethanesulfonamide) and fuming nitric acid,N,N-hexamethylenebis(N-nitroethanesulfonamide). The product is a whitecrystalline solid melting at 66-68 C.

From N,N-ethylenebis(l-propanesulfonamide) and ni troniumtetrafluoroborate, with nitromethane as inert liquid reaction medium,N-nitro-N,N'-ethylenebis(l-propanesulfonamide) product having amolecular weight of 317.4.

From N,N' hexamethylenebis(methanesulfonamide) and fuming nitric acid,N,N'-hexamethylenebis(N-nitromethanesulfonamide) product melting at97.5-98.5 C.

From N,N'-decamethylenebis(3-carbomethoxy-5-nitrobenzenesulfonamide) andfuming nitric acid, N,N'-decamethylenebis(3 carbomethoxy N,5dinitrobenzenesulfonamide) product having a molecular weight of 720.7.

From N,N hexamethylenebis(benzenesulfonamide) and fuming nitric acid, asolid N,N"-hexamethylenebis- (N-nitrobenzenesulfonamide) product meltingat 141- 142 C.

From N,N' decamethylenebis(methanesulfonamide) and nitroniumtetrafiuoroborate, with methylene chloride as inert liquid reactionmedium, N-nitro-N,N-decamethylenebis(methanesulfonamide) product havinga molecular weight of 373.5.

From N,N' pentamethylenebis(methanesulfonamide) and fuming nitric acid,N,N'-pentamethylenebis(N-nitromethanesulfonamide) product. The productis a white crystalline solid melting at 85-86 C.

From N,N 1,4-cyclohexylenebis(S-bromo-m-toluenesulfonamide) and fumingnitric acid, N,N'-l,4-cyclohexylenebis(Nnitro-S-bromo-m-toluenesulfonamide) product (molecular weight of 670.4).

From N,N decamethylenebis(2,4,5-trichlorobenzenesulfonamide) and fumingnitric acid,N,N'-decamethylenebis(N-nitro-2,4,5-trichlorobenzenesulfonamide) product(molecular weight of 749.3).

From N,N' pentamethylenebis(benzenesulfonamide) and fuming nitric acid,N,N'-pentamethylenebis(N-nitrobenzenesulfonamide) product melting at113-114 C.

From N,N-l,4-cyclohexylenedimethylenebis(benzenesulfonamide) and fumingnitric acid, in acetic anhydride, N nitro N,N 1,4cyclohexylenedimethylenebis(benzenesulfonamide) product having amolecular weight of 467.6.

From N,N'-ethylenebis(ethanesulfonamide) and fuming nitric acid,N,N-ethylenebis(N-nitroethanesulfonamide) product. The product melts at16l163 C.

From N,N' (1 propyltrimethylene)bis(p-bromobenzenesulfonamide) andfuming nitric acid, N,N'-(l-propyltrimethylene)bis(N-nitro pbromobenzenesulfonamide) product having a molecular weight of 644.4.

From N,N' ethylenebis(1 butanesulfonamide) and fuming nitric acid,N,N'-ethylenebis(N-nitro-l-butanesulfonamide) product melting at 55.557C.

From N,N' 2 butenylenebis (para chlorobenzenesulfonamide) and fumingnitric acid, in acetic anhydride, N-nitro-N,N' 2butenylenebis(para-chlorobenzenesulfonamide) having a molecular weightof 480.4.

From N,N' ethylenebis(3,4 dichlorobenzenesulfonamide) and fuming nitricacid, N,N'-ethylenebis(3,4-dichloro-N-nitrobenzenesulfonamide) productmelting, with decomposition, at 168-170 C.

From N,N' 1,2 cyclohexylenebis(3,4,5-trimethylbenzenesulfonamide) andfuming nitric acid, N,N'-l,2-cyclohexy1enebis(N nitro 3,4,5trimethylbenzenesulfonamide) product (molecular weight of 568.7).

From N,N' ethylenebis(m-nitrobenzenesulfonamide) and fuming nitric acid,N,N'-ethylenebis(N,m-dinitrobenzenesulfonamide) product. The productmelts, with decomposition, at 185 C.

From N,N nonamethylenebis(methanesulfonamide) and fuming nitric acid, awhite crystalline N,N-nonamethylenebis (N nitromethanesulfonamide)product melting at 6769 C.

From N,N hexamethylenebis(meta toluenesulfonamide) and nitroniumtetrafiuoroborate, N-nitro-N,N'- hexamethylenebis(metatoluenesulfonamide) product having a molecular weight of 469.6.

From N,N-hexamethylenebis 3,4-dichlorobenzenesulfonamide) and fumingnitric acid N,N'-hexamethylenebis (3,4-dichloro Nnitrobenzenesnlfonamide) product. The product melts at 142l44 C.

From N,N propylenebis(3,5 dinitrobenzenesulfonamide) and fuming nitricacid, N,N'-propylenebis(N,3,5- trinitrobenzenesulfonamide) product(molecular weight of 624.5).

From N,N ethylenebis(3-nitro-p-t0luenesulfonamide) and fuming nitricacid, N,N' ethylenebis(N,3-dinitro-ptoluenesulfonamide) product whichmelts, with decomposition, at 183 C.

From N,N-pentamethylenebis(2,3,4,5-tetramethylbenzenesulfonamide) andfuming nitric acid, N,N'-pentamethylenebis(2,3,4,5 tetramethyl Nnitrobenzenesulfonamide) product having a molecular weight of 584.7.

From N,N (1,4 cyclohexylenedimethylene)bis (benzenesulfonamide) andfuming nitric acid, white crystalline N,N' (1,4cyclohexylenedimethylene)bis(N-nitrobenzenesulfonamide) product. Theproduct melts, with decomposition, at C.

From N,N-hexamethylenebis(m-nitrobenzenesulfonamide) and fuming nitricacid, N,N'-hexamethylenebis- (N,m-dinitrobenzenesulfonamide) productmelting, with decomposition, at 166 C.

From N,N'-ethylenebis(3-ethyl-5-isopropylbenzenesulfonamide) and turningnitric acid, N,N'-ethylenebis(3- ethyl-5-isopropyl Nnitrobenzenesulfonamide) product having a molecular weight of 570.

From N,N-hexamethylenebis(3 nitro p toluenesulfonamide) and fumingnitric acid, N,N'-hexamethylenebis(N,3-dinitro-p-toluenesulfonamide)product melting at 159-160 C.

It has been discovered that the compounds of the present invention areuseful in a wide variety of operations, for the modification andalteration of the growth of numerous organisms such as, for example,mite, tick, helminth, bacterial, fungal, plant, and insect organisms. Insuch operations, a growth altering and/or pesticidal amount of at leastone of the nitrosulfonamide compounds is employed.

It has been further discovered that the exposure of a viable form ofplants to the action of nitrosulfonamide compound gives rise todifferent responses depending upon the nature of the plant, the stage ofgrowth or maturity of the plant, and the dosage of nitrosulfonamidecompound at which the exposure is carried out. Thus,

the application to plants, plant parts, and their habitats of aherbicidal amount of nitrosulfonamide com-pound suppresses and inhibitsthe growth of seeds, emerging seedlings, and established vegetation. Theapplication to plants of a lesser and growth-stimulant amount ofnitrosulfonamide compound imparts beneficial elfects to the growth ofthe plants, such as, for example, increased size of produce, or of yieldof crop; earlier plant maturation; improved qualitative content of plantparts, such as protein content in legumes and in members of theGramineae family; delayed senescence; and the like. The application ofnitrosulfonamide compound to plants may be made by contacting thecompound with seeds, seedlings, established vegetation, roots, stems,flowers, fruits, and the like, or by applying the compound to soil.

The application to the organisms or their habitats of a growth alteringamount of nitrosulfonamide compound is essential and critical for thepractice of the present inven tion. The exact dosage ttO be supplied isdependent upon the organism, the stage of growth thereof, and, in manyinstances, the particular part of the organism to which thenitrosulfonamide compound is applied. Where parasite control is desired,the compounds are employed in parasiticidal amounts. Where the inventionis employed to modify and alter the growth of plants, and plant parts,the compounds are employed in plant growth altering amounts, forexample, nitrosulfonamide compound can be applied to plants, plantparts, and their habitats in herbicidal dosages. In foliar applicationsof herbicidal dosages, liquid compositions containing from about 4,000or less to 20,000 or more parts of nitrosulfonamide compound by weightper million parts of ultimate composition can be conveniently applied toplant surfaces. In the application to growth media of herbicidal dosagesof nitrosulfonamide compound, good results are obtained when thecompound is supplied to the growth media in an amount of from about 5 to300 parts or more by weight per million parts by weight of the media.Where the growth media is soil, good results are obtained when thenitrosulfonamide compound i distributed therein at a rate of from about20 or less to 300 pounds or more per acre and through such a crosssection of the soil as to provide for the presence therein ofnitrosulfonamide compound in an amount of from 20 to 300 parts permillion. In such application, it is desirable that the compound bedistributed to a depth of at least 0.5 inch and at a substantiallyuniform dosage of at least 10 pounds per acre inch of soil. Theweathering action of the sun, rain, and possibly the dccomposition ofthe agents by the action of soil organisms eventually reduces theirconcentration in soil, or other growth media.

In other applications of the present nitrosulfonamide compounds, theactive agents are employed in plant growth stimulating dosages. In suchoperations, good results are obtained when the compounds are applied toplants and plant parts in dosages of from 0.001 or less to 20 or morepounds per acre. In other similar operations, liquid compositionscontaining from about 1 to 4,000 or more parts per million can beconveniently applied to the plant surfaces. In the treatment of seed tostimulate seedling growth and obtain improved yield of the plantsproduced by such seeds, good results are obtained when the seeds aretreated with from about 1 to 250 grams (about 0.035 to 9 ounces) ofcompound per hundred pounds of seed.

The method of the present invention can be carried out by exposing theorganisms, or their habitats, to the action of the unmodified compounds.The present method also comprehends the employment of a liquid or dustcomposition containing one or more of the present compounds as an activecomponent. In such usage, the active component is modified with one or aplurality of additaments or adjuvants for organism growth modificationcompositions, such as water or other liquid carriers, surfaceactivedispersing agents, and finely divided solids. Depending upon theconcentration of active compound, such augmented compositions areadapted to be applied to the organisms and their habitats, or to beemployed as concentrates and subsequently diluted with additional inertcarrier to produce the ultimate treating compositions. In compositionswhere the adjuvant or helper is a finely divided solid, a surface-activeagent or a liquid additament, the carrier cooperates with the activecomponent so as to facilitate the invention, and to obtain an improvedand out standing result.

In addition, the present method also comprehends the employment ofaerosol compositions containing one or more of the present compounds asan active agent. Such compositions are prepared according toconventional methods wherein the agent is dispersed in a solvent and theresultant dispersion mixed with a propellant in liquid state. Suchvariables as the particular compound to be used and the particularsubstrate to be treated will determine the identity of the solvent andthe concentration of the active compound. The solvent should be of lowphytotoxicity, such as water, acetone, isopropanol or 2-ethoxyethanol,in compositions to be applied to plants for plant stimulation and cropyield improvement.

The exact concentration of the active compound to be employed in thetreating compositions is not critical and can vary considerably providedthe required dosage of effective agent is supplied upon the organism orits habitat. The concentration of the active agent in liquidcompositions employed to supply the desired dosage generally is fromabout 0.0001 to 50 percent by weight. Concentrations of up to 95 percentby Weight are oftentimes conveniently employed. In dusts, theconcentration of active component can be from about 0.01 to 20 percentby weight. In compositions to be employed as concentrates, the activecomponent can be present in a concentration of from about 5 to 98percent by weight.

The quantity of the composition applied is not critical provided onlythat the required dosage of active component is applied in sufi'icientof the finished composition to cover adequately the organism or habitatto be treated.

Liquid compositions containing the desired amount of active componentcan be obtained by dissolving the compound in an organic liquid carrieror by dispersing the active agent in water. With the water-insolubleagents, the dispersion is facilitated and conveniently accomplished withthe aid of a suitable surface-active dispersing agent such as an ionicor non-ionic emulsifying agent. The aqueous compositions can contain oneor more water-immiscible solvents for the active agent. In suchcompositions, the carrier can comprise an aqueous emulsion, that is, amixture of water-immiscible solvents, emulsifying agent and water. Thechoice of dispersing and emulsifying agent and the amount thereofemployed is dictated by the nature of the composition type and by theability of the agent to facilitate the dispersion of the active agent inthe carrier to produce the desired composition. Dispersing andemulsifying agents which can be employed in the compositions include thecondensation products of alkylene oxides with phenols and organic acids,alkyl aryl sulfonates, polyoxyethylene derivatives of sorbitan esters,complex alcohols, mahogany soaps and the like.

In the preparation of dust compositions, the active component isdispersed in and on a finely divided solid which is non-reactive withthe active agent. Suitable finely divided solids are talc, chalk,gypsum, and the like. In such operations, the finely divided carrier ismixed with the active compound or a volatile organic solvent solutionthereof. Similarly, dust compositions containing the active compoundsare prepared from various of the solid surface-active dispersing agents,such as bentonite, fullers earth, attapulgite and other clays. Dependingupon the proportion of ingredients, the dust compositions can beemployed as concentrates and subsequently diluted with additional solidsurface-active dispersing agent or with talc, chalk, or gypsum and thelike to ob tain the desired amount of active component in compositionsadapted to be applied to the organisms or their habitats. Also, suchconcentrated dust compositions can be dispersed in water with or withoutthe aid of a dispersing agent, to form spray mixtures. Preferred finelydivided solid adjuvants include those which are of low phytotoxicity toplants and plant parts.

When operating in accordance with the present invention, the activeagents or compositions containing the agents are applied to theorganisms or their habitats in growth-modifying amounts in anyconvenient fashion, for example, with power clusters, boom and handsprayers, and spray dusters. In another procedure, the agents orcompositions containing the same are drilled into soil and furtherdistributed therein in conventional procedures.

The following examples illustrate the best manner of employing thepresent invention, and, without more, will enable those skilled in theart to employ the method of the present invention.

Example 4 Compositions containing the compounds of the present inventionare prepared in various procedures. In one procedure, four parts byweight of one of the nitrosulfonamide compounds, 0.08 part of sorbitantrioleate (Span 85) and 0.02 part of a sorbitan monolauratepolyoxyethylene derivative (Tween are dispersed in forty milliliters ofacetone to produce a concentrate composition in the form of awater-dispersible liquid.

In another procedure, one of the nitrosulfonamide compounds isformulated in water with an alkyl aryl sulfonate (Nacconol NR) and asubstituted benzoid alkyl sulfonic acid (Daxad No. 27) to produceaqueous com positions. In such operations, the materials are ballrnilledtogether to produce compositions containing varylng amounts of one ofthe active agents, 300 parts by weight of Nacconol NR and 300 parts byweight of Daxad No. 27 per million parts by weight of ultimate aqueousmixture. In this manner, ballmilled compositions are prepared from allof the nitrosulfonamide compounds of the above examples.

Example 5 Liquid compositions are prepared with N,N' pentamethylenebis(Nnitrobenzenesulfonamide), N,N pentamethylenebis(Nnitromethanesulfonamide), N,N"- ethylenebis(N nitroethanesulfonamide),N,N hexamethylenebis(N nitroethanesulfonamide), N,N hexamethylenebis(3,4dichloro N nitrobenzenesulfonamide), and N,N ethylenebis(N,3 dinitroptoluenesulfonamide) in the ballmilling procedure described in Example 4and each containing an amount of one of the named active agents.

These compositions are employed for the treatment of seed beds of sandyloam soil of good nutrient content. Prior to the treatment, the soil isseeded with the seeds of peas (Pisum sativum) and beans (Phaseolusvulgaris). In the treating operations, the composition is applied as asoil drench and at a rate of about 0.434 acre inch of aqueouscomposition per acre to supply varying amounts of one of the compoundsper acre and varying concentrations of one of the compounds in the soil.Other areas similarly seeded with the named plant species are leftuntreated to serve as checks. Following the treating operations, theseed beds are observed at regular intervals to ascertain any appreciableeffects upon the germination of the seeds and the growth of theseedlings.

Two weeks following the treating operations, the average height of theplants above the ground line in the treated seed beds is measured andcompared with the average height above the ground line of the plants inthe untreated seed beds. At the time of the measurements, all of thetreated and untreated seed beds support abundant stands of healthyplants of the named species. The results of the measurements, theagents, and the concentrations and dosages at which the agents areemployed are set forth in the following table.

Percent greater stem elongation of treated pea plants than of untreatedpea plants Test compound:

N,N'-ethylenebis(N nitroethanesulfonamide) 22 N,N'-ethylenebis(N nitro 1butanesulfon- Example 7 Liquid compositions are prepared withN,N'-t6tr-arnethylenebis( N nitrom'ethanesulfonamide),N,N'-ethylenebis(N-nitrobenzenesulfonamide), andN,N'-ethylenebis(N-nitro-l-butanesulfonamide) in the ballmillingprocedure described in Example 4 and each containing an amount of one ofthe named active agents.

Percent Greater Stem Elongation of Plants from Treated Soil than fromConcentration of Dosage of Test Com ounds U t d S '1 Test Compound TestCompound p ntrea e m in Composition Parts per Pounds million Peas Beansper acre by weight;

of soil N,N-pentamethylenebis(N-nittobenzenesulfonamide) 0.0086 1 1.6 4625 N,N-pentamethylenebis(N-nitromethanesulionamide) 0. 0086.. 1 1,6 2615 N,N'ethy1enebis(N nitroethanesultonamide) {8' 3233 g 6 3 23N,N-hexametl1ylenebis(N-nitroethanesulfonarnide) 0. 0086 1 1.6 26N,N-hexamethylenebis(3, 4-dichloro-N-nitrobenzenesultonamide) 0. 0432" 58 114 30 N,N'-ethy1enebis(N,3-dinitro-p-toluenesulfonamide) ..{8' 82 3 61}: 3%

Example 6 Also, concentrate composition is prepared as described AqueousSpray composition each containing 100 Parts 4 in Example 4 fromN,N'-hexamethylenebis(N-nitromethby weight of one of variousnitrosulfonamide compounds per million parts by weight of ultimatemixture are prepared in accordance with the foregoing examples. Thesecompositions are employed in post emergent applications for thetreatment of pea plants (Pisum sativum). In the treating operations, thecompositions are applied as foliage sprays to plots of the pea plants.At the time of the applications, the plants are from two to four inchesin height. The treatments are carried outwith conventionalanesulfonamide) and the resulting concentrate dispersed in Water toprepare an aqueous composition containing an amount of the named activeagent.

In procedures essentially identical with those employed in Example 5,these aqueous compositions are employed for the planlt growthmodification of bean plants. The results of the measurements togetherwith the agents, concentrations, and dosages at which they are employedare set forth in the following table.

Test Compound Concentration of Percent Greater Stem Dosage of TestCompounds Elongation or Bean Plants Test Compound Pounds per Parts perfrom Treated Soil than from in Composition acre million by UntreatedSoil weight of soil N,N-hexamethylenebis(N-nitromethanesultonamide)0.0432... 5 8 21 N,N-tetramethylenebis(N-nitromethanesulfonamide) 0.00S61 1.6 N,N-ethylenebis(N-nitrobenzenesulfonamide) 6 I 0.0086. 1 1.6 36N,N -ethyleneb1s(N-nitro-l-butanesulfonarmde) 0 0432 5 8 72 Thehydrocarbonylenedisulfonamide starting material is prepared in knownprocedures in which a hydrocarbonylenediamine compound of the formula isreacted :with a sulfonyl chloride compound of the formula R'SO Cl in thepresence of a hydrogen halide acceptor.

The reaction is conveniently carried out in the presence of an inertliquid reaction medium, for example, Water,

benzene, chloroform, methylene chloride, carbon tetrachloride, andhexane. The amounts of the reactants to be employed are not critical,desired product compound being obtained when employing the reactants inany amounts. The reaction consumes the reactants in amounts whichrepresent one molecular proportion of hydrocarbonylenediamine compound,two molecular proportions of sulfonyl chloride compound, and twomolecular proportions of hydrogen halide acceptor. Higher yields resultfrom use of one molecular proportion of hydrocarbonylenediaminecompound, four or more molecular proportions of sulfonyl chloridecompound, and two or more molecular proportions of hydrogen halideacceptor, and the use of such proportions is preferred.

The hydrogen halide acceptor can be of any of those conventionallyemployed in organic synthesis; for example, an alkali metal hydroxide, atertiary amine, pyridine, and the like. It is sometimes convenient toemploy the hydrogen halide acceptor in large excess so that it servesboth as hydrogen halide acceptor and as solvent for the reactants.

The reaction takes place smoothly at temperatures between and 100 C.,and preferably, at temperatures of between 10 and 45 C., with theproduction of the desired product compound in the reaction mixture. Incarrying out the reaction, the reactants and the hydrogen halideacceptor are contacted together in any convenient fashion and maintainedfor a period of time within the reaction temperature range to completethe reaction. The yield of desired product compound is increased bypermitting the reaction mixture to stand for a period of time. Followingthe completion of the reaction, the desired reactant material can beseparated and purified, according to procedures known by those skilledin the art.

I claim:

1. Method of stimulating plant growth which comprises applying to plantsand plant parts a plant growth-stimulating amount of compound of theformula N02 R" R-S 2I IRI IS 2R wherein R represents a divalenthydrocarbonylene radical selected from the group consisting of alkylenebeing of from 2 to 10, inclusive, carbon atoms, 2-butenylene,cyclohexylene, and cyclohexylenedimethylene; R represents a memberselected from the group consisting of loweralkyl being of from 1 to 4,inclusive, carbon atoms, phenyl, and phenyl radical which is ringsubstituted with one or more substituent moieties selected from thegroup consisting of halo, loweralkyl, nitro, and carboloweralkoxy, therebeing up to and including five substituent moieties when everysubstituent moiety is selected from the group consisting of halo andloweralkyl, and there being one or two substituent moieties when one ofthe substituent moieties is selected from the group consisting of nitroand carboloweralkoxy; and R" represents a member selected from the groupconsisting of hydrogen and nitro.

2. Plant growth-stimulating composition comprising from 5 to 98 percentby weight of an active ingredient in admixture with a surface activeagent and a finely divided solid, the active ingredient being compoundof the formula wherein R represents a divalent hydrocarbonylene radicalselected from the group consisting of alkylene being of from 2 to 10,inclusive, carbon atoms, 2-butenylene, cyclohexylene, andcyclohexylenedimethylene; R represents a member selected from the groupconsisting of loweralkyl being of from 1 to 4, inclusive, carbon atoms,phenyl, and phenyl radical which is ring substituted with one or moresubstituent moieties selected from the group consisting of halo,loweralkyl, nitro, and carboloweralkoxy, there being up to and includingfive substituent moieties when every substituent moiety is selected fromthe group consisting of halo and loweralkyl, and there being one or twosubstituent moieties when one of the substituent moieties is selectedfrom the group consisting of nitro and carboloweralkoxy; and R"represents a member selected from the group consisting of hydrogen andnitro.

3. The composition which comprises an aqueous dispersion of thecomposition claimed in claim 2, the active ingredient in suchcomposition being present in the amount of at least 0.0001 percent byweight.

References Cited UNITED STATES PATENTS 3/1958 Glahn et al. 260-556 X9/1962 Hunter 260-556 X OTHER REFERENCES JAMES O. THOMAS, JR., PrimaryExaminer.

